Terpolymers of 2-acrylamido-2-methylpropane-sulfonic acid, sodium salt (AMPS), N,N-dimethylacrylamide, and acrylonitrile

ABSTRACT

Novel water-soluble terpolymers comprising: -Ingredients Mole % -2-acrylamido-2-methylpropane- 51-59 -sulfonic acid, sodium salt (AMPS) -N,N-dimethylacrylamide  6-28 -acrylonitrile 20-35 -  These terpolymers provide high temperature fluid loss additives and rheology stabilizers for high calcium-containing brine clay drilling fluids.

INTRODUCTION

This application is a divisional application of Ser. No. 530,569, filed Sept. 9, 1983, now U.S. Pat. No. 4,502,964.

A serious problem is encountered when clay-based oil well drilling fluids are subjected to conditions of high temperature and high pressure in conjunction with utilization of high calcium-containing brines which are used to prepare these drilling fluids. When these conditions exist, conventional drilling fluid polymeric additives such as acrylamide polymers, when used as stabilizers for these fluids, tend to be rendered ineffective.

Recently a partial solution to the problem has been provided by the utilization as a fluid loss additive and rheology stabilizer a terpolymer composed of:

    ______________________________________                                         Ingredients           Mole %                                                   ______________________________________                                         2-acrylamido-2-methylpropane-                                                                        52.0                                                     sulfonic acid, sodium salt (AMPS)                                              acrylamide            32.0                                                     N--methyl-N--vinyl acetamide                                                                         16.0                                                     ______________________________________                                    

This terpolymer, while proving to be effective as a high temperature fluid loss additive for oil well drilling fluids, has the disadvantage of using in its composition 16.0 mole % of N-methyl-N-vinyl acetamide. This renders the material expensive to use.

If it were possible to use a polymeric high temperature fluid loss additive and rheology stabilizer that was resistant to high calcium-containing brines, an improvement in the art would be afforded.

THE INVENTION

The invention comprises the utilization of a terpolymer with the following composition:

    ______________________________________                                                           Mole %                                                       Ingredients         Preferred                                                                               General                                           ______________________________________                                         2-acrylamido-2-methylpropane-                                                                      53.5     51-59                                             sulfonic acid, sodium salt (AMPS)                                              N,N--dimethylacrylamide                                                                            16.6      6-28                                             acrylonitrile       29.8     20-35                                             ______________________________________                                    

As will be shown hereafter, these terpolymers provide excellent high temperature fluid loss protection to a clay-based bring prepared drilling fluid.

These terpolymers may be prepared in accordance with the following preparative technique, illustrating the preparation of the preferred terpolymer listed above:

A polymerization vessel was fitted with a stirrer, thermometer, condenser and addition port. The vessel was charged with 325 g of water, 53 g of 2-acrylamido-2-methylpropanesulfonic acid, 21 g of a 50% solution of sodium hydroxide, 8 g of N,N-dimethylacrylamide and 7.6 g of acrylonitrile (ACN). The pH was adjusted to 8.3 and the polymerization was initiated by the sequential addition of 10 ml of a 0.5% solution of sodium bisulfite and 10 ml of a 0.5% solution of ammonium persulfate. After two hours reaction time at room temperature, the temperature was raised to 75° C. for one hour. After cooling, the polymer solution had a Brookfield viscosity of 96,000 cps.

The amount of polymer used to stabilize clay-based drilling fluids under conditions of high temperature and pressure may vary between about 10% up to 60% by weight based on the clay present in the field.

The polymers may be further characterized as having a molecular weight below 1,000,000. Preferably, they have a molecular weight within the range of 10,000-500,000.

To illustrate the invention, the preferred composition shown above was tested in a high temperature, high pressure fluid loss additive test which is described in detail in the American Petroleum Institute publication, RP13(B).

The particular drilling fluid tested contained 15 pounds/barrel of a pre-hydrated Bentonite drilling fluid clay and a 50% dilution of a brine known as a Williston Basin brine. This brine contained a substantial amount of calcium.

The blank test produced a filtrate of 42 ml/7.5 min.

The preferred composition of the invention was added to provide 6 pounds/barrel of active polymer. This provided an approximate dosage of 40% by weight active polymer based on active clay. At the end of 30 minutes, the fluid loss in the above described test was 16 ml.

Using the same preparative technique and test method for determining fluid loss additive effectiveness, the following additional polymers were prepared and tested:

    ______________________________________                                                             N,N--dimethyl                                                                              HTHP                                           AMPS    ACN         acrylamide  Fluid Loss                                     ______________________________________                                         53.5    29.8        16.6        16 ml.                                         58.7    34.8         6.5        17 ml.                                         51.2    20.8        28.0        30 ml.                                         ______________________________________                                     

Having thus described our invention, it is claimed as follows:
 1. A novel water-soluble terpolymer having a molecular weight below 1,000,000 comprising:

    ______________________________________                                         Ingredients           Mole %                                                   ______________________________________                                         2-acrylamido-2-methylpropane-                                                                        51-59                                                    sulfonic acid, sodium salt (AMPS)                                              N,N--dimethylacrylamide                                                                               6-28                                                    acrylonitrile         20-35                                                    ______________________________________                                    


2. A novel water-soluble terpolymer comprising:

    ______________________________________                                         Ingredients           Mole %                                                   ______________________________________                                         2-acrylamido-2-methylpropane-                                                                        53.5                                                     sulfonic acid, sodium salt (AMPS)                                              N,N--dimethylacrylamide                                                                              16.6                                                     acrylonitrile         29.8                                                     ______________________________________                                    


3. The novel water-soluble terpolymer of claim 1 wherein the molecular weight is within the range of 10,000-500,000. 